EP3049455B1 - Nouveaux agents de réticulation pour matières de revêtement - Google Patents

Nouveaux agents de réticulation pour matières de revêtement Download PDF

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Publication number
EP3049455B1
EP3049455B1 EP14766119.3A EP14766119A EP3049455B1 EP 3049455 B1 EP3049455 B1 EP 3049455B1 EP 14766119 A EP14766119 A EP 14766119A EP 3049455 B1 EP3049455 B1 EP 3049455B1
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Prior art keywords
groups
group
ketone
methyl
polyisocyanate
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EP14766119.3A
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German (de)
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EP3049455A1 (fr
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Frederic Lucas
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BASF SE
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BASF SE
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D175/00—Coating compositions based on polyureas or polyurethanes; Coating compositions based on derivatives of such polymers
    • C09D175/04—Polyurethanes
    • C09D175/12—Polyurethanes from compounds containing nitrogen and active hydrogen, the nitrogen atom not being part of an isocyanate group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/2805—Compounds having only one group containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/302—Water
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/302—Water
    • C08G18/307—Atmospheric humidity
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/80—Masked polyisocyanates
    • C08G18/8061—Masked polyisocyanates masked with compounds having only one group containing active hydrogen
    • C08G18/807—Masked polyisocyanates masked with compounds having only one group containing active hydrogen with nitrogen containing compounds

Definitions

  • the present invention describes new crosslinkers for coating compositions, their production and their use.
  • blocked isocyanates is that after the isocyanates have been deblocked by heating, the blocking agents are driven out of the coating and thus lead to emissions or, if they remain in the coating, can lead to discoloration, secondary reactions, clouding or blistering.
  • Example 2 discloses thermally curable compositions and their use as coatings.
  • IPDI is first reacted with a secondary amine (bis (3-triethoxysilylpropyl) amine).
  • Glycidol is then metered into the resulting mixture until no more isocyanate groups can be detected.
  • Example 2 discloses the production of a coating material based on the PUR system produced in Production Example 2.
  • compositions which contain at least one polyurethane according to the invention and optionally solvent, optionally at least one catalyst and / or optionally additives typical of paints. At least one solvent is preferably present.
  • coating compositions according to the invention that even thick layers can be cured without bubbles using the coating compositions according to the invention.
  • Another advantage of the present invention is that the blocking agents used from the blocked polyisocyanates in the coating compositions according to the invention are not released from the coating, but rather are captured. Thus the emissions of the cured coatings are reduced.
  • At least one aliphatic or cycloaliphatic di- or polyisocyanate At least one aliphatic or cycloaliphatic di- or polyisocyanate.
  • the monomeric isocyanates used for the preparation of the polyisocyanates can be aromatic, aliphatic or cycloaliphatic, preferably aliphatic or cycloaliphatic, which is referred to as (cyclo) aliphatic for short in this document; aliphatic isocyanates are particularly preferred.
  • Aromatic isocyanates are those which contain at least one aromatic ring system, i.e. both purely aromatic and araliphatic compounds.
  • Cycloaliphatic isocyanates are those which contain at least one cycloaliphatic ring system. Aliphatic isocyanates are those that contain exclusively straight or branched chains, i.e. acyclic compounds.
  • the monomeric isocyanates are preferably diisocyanates which have exactly two isocyanate groups. In principle, however, they can also be monoisocyanates with an isocyanate group.
  • higher isocyanates with an average of more than 2 isocyanate groups are also suitable.
  • triisocyanates such as triisocyanatononane, 2'-isocyanatoethyl- (2,6-diisocyanatohexanoate), 2,4,6-triisocyanatotoluene, triphenylmethane triisocyanate or 2,4,4'-triisocyanatodiphenyl ether or mixtures of di-, tri- and higher are suitable
  • Polyisocyanates which are obtained, for example, by phosgenation of corresponding aniline / formaldehyde condensates and which are polyphenyl polyisocyanates containing methylene bridges, in particular triisocyanatononane and 2'-isocyanatoethyl (2,6-diisocyanatohexanoate).
  • the monomeric isocyanates are preferably isocyanates having 4 to 20 carbon atoms.
  • Examples of common diisocyanates are aliphatic diisocyanates such as tetramethylene diisocyanate, 1,5-pentamethylene diisocyanate, hexamethylene diisocyanate (1,6-diisocyanatohexane), octamethylene diisocyanate, decamethylene diisocyanate, dodecamethylene diisocyanate, tetradecamethylene diisocyanate, derivatives of lysine diisocyanate (e.g.
  • methyl-2,6-diisocyanate Trimethylhexane diisocyanate or tetramethylhexane diisocyanate
  • cycloaliphatic diisocyanates such as 1,4-, 1,3- or 1,2-diisocyanatocyclohexane, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane, 1-isocyanato-3,3,5 -trimethyl-5- (isocyanatomethyl) cyclohexane (isophorone diisocyanate), 1,3- or 1,4-bis (isocyanatomethyl) cyclohexane or 2,4- or 2,6-di-isocyanato-1-methylcyclohexane and 3 (or 4), 8 (or 9) -bis (isocyanatomethyl) -tricy-clo [5.2.1.02.6] decane isomer mixtures, as well as aromatic diisocyanates such as 2,4- or
  • 1,6-hexamethylene diisocyanate 1,3-bis (isocyanatomethyl) cyclohexane, isophorone diisocyanate and 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane are particularly preferred, isophorone diisocyanate and 1,6-hexamethylene diisocyanate are very particularly preferred, 1,6-hexamethylene diisocyanate is particularly preferred.
  • Isophorone diisocyanate is mostly in the form of a mixture, namely the cis and trans isomers, generally in a ratio of about 60:40 to 90:10 (w / w), preferably from 70:30 to 90:10.
  • Dicyclohexylmethane-4,4'-diisocyanate can also be present as a mixture of the various cis and trans isomers.
  • (cyclo) aliphatic diisocyanates such as 1,6-hexamethylene diisocyanate (HDI), isomeric aliphatic diisocyanates with 6 carbon atoms in the alkylene radical, 4,4'- or 2,4'-di (isocyanatocyclohexyl) methane and 1-isocyanato- 3-isocyanato-methyl-3,5,5-trimethyl-cyclohexane (isophorone diisocyanate or IPDI) are produced by reacting the (cyclo) aliphatic diamines with, for example, urea and alcohols to form (cyclo) -aliphatic biscarbamic acid esters and their thermal cleavage into the corresponding Diisocyanates and alcohols.
  • HDI 1,6-hexamethylene diisocyanate
  • IPDI isophorone diisocyanate
  • the synthesis usually takes place continuously in a cycle process and optionally in the presence of N-unsubstituted carbamic acid esters, dialkyl carbonates and other by-products recycled from the reaction process.
  • Diisocyanates obtained in this way generally have a very low or even non-measurable proportion of chlorinated compounds, which is advantageous, for example, in applications in the electronics industry.
  • the isocyanates used have less than 100 ppm, preferably less than 50 ppm, in particular less than 30 ppm and especially less than 20 ppm, of hydrolyzable chlorine. This can be measured, for example, by ASTM regulation D4663-98.
  • the total chlorine contents are, for example, below 1000 ppm, preferably below 800 ppm and particularly preferably below 500 ppm (determined by argentometric titration after hydrolysis).
  • mixtures of such monomeric isocyanates which have been obtained by reacting the (cyclo) aliphatic diamines with, for example, urea and alcohols and cleavage of the (cyclo) aliphatic biscarbamic acid esters obtained, with such diisocyanates which have been obtained by phosgenation of the corresponding amines, can be used.
  • the polyisocyanates to which the monomeric isocyanates can be oligomerized are generally characterized as follows:
  • the average NCO functionality of such compounds is generally at least 1.8 and can be up to 8, preferably 2 to 5 and particularly preferably 2.4 to 4.
  • the polyisocyanate is selected from the group consisting of isocyanurates, biurets, urethanes and allophanates, preferably from the group consisting of isocyanurates, urethanes and allophanates, particularly preferably a polyisocyanate containing isocyanurate groups.
  • the polyisocyanate is polyisocyanates containing isocyanurate groups and derived from 1,6-hexamethylene diisocyanate and / or isophorone diisocyanate, very particularly preferably based on 1,6-hexamethylene diisocyanate.
  • the polyisocyanate is a mixture of polyisocyanates containing isocyanurate groups, very particularly preferably 1,6-hexamethylene diisocyanate and isophorone diisocyanate.
  • the polyisocyanate is a mixture containing low-viscosity polyisocyanates, preferably polyisocyanates containing isocyanurate groups, with a viscosity of 600-1500 mPa * s, in particular below 1200 mPa * s, low-viscosity urethanes and / or allophanates with a viscosity from 200-1600 mPa * s, in particular 600-1500 mPa * s, and / or polyisocyanates containing iminooxadiazinedione groups.
  • the viscosity is specified at 23 ° C. in accordance with DIN EN ISO 3219 / A.3 in a cone-plate system with a speed gradient of 1000 s -1 , unless otherwise noted.
  • component (A) is a diisocyanate selected from the group consisting of isophorone diisocyanate, 2,4'-di (isocyanatocyclohexyl) methane and 4,4'-di (isocyanatocyclohexyl) methane and their Mixtures, particularly preferably selected from the group consisting of isophorone diisocyanate and 4,4'-di (isocyanatocyclohexyl) methane.
  • component (A) is a polyisocyanate selected from the group consisting of polyisocyanates containing isocyanurate groups based on 1,6-hexamethylene diisocyanate and polyisocyanates containing biuret groups based on 1,6-hexamethylene diisocyanate.
  • the compound (B) is at least one, for example one to three, preferably one to two and particularly preferably exactly one compound with at least one, for example one to three, preferably one to two and particularly preferably exactly one isocyanate-reactive group and at least one, preferably one to three, particularly preferably one to two and very particularly preferably exactly one epoxy group.
  • Groups reactive towards isocyanate are hydroxyl or thiol groups, preferably hydroxyl groups.
  • Methylene and 1,2-ethylene are particularly preferred.
  • R 2 is very particularly preferably methylene.
  • Preferred compounds (B) are glycerol diglycidyl ether, in particular its mixture of compounds with free primary and free secondary hydroxyl groups, trimethylolpropane diglycidyl ether, pentaerythritol triglycidyl ether and glycidol, glycidol being particularly preferred.
  • the compounds (C) are those compounds which are known as blocking agents for blocking free isocyanate groups and which are additionally reactive with an epoxy group, i. able to open an epoxy group.
  • classes of compounds used for blocking are phenols, imidazoles, triazoles, pyrazoles, oximes, N-hydroxyimides, hydroxybenzoic acid esters, secondary amines, lactams, CH-acidic cyclic ketones, malonic acid esters or alkyl acetoacetates.
  • the blocking agents (C) are particularly preferably the secondary amines, oximes, pyrazoles and 1,3-dicarbonyl compounds listed above, very particularly preferably diisopropylamine, 2,6-dimethylpiperidine, 2,2,6 , 6-tetramethylpiperidine, butanone oxime, diethyl malonate and ethyl acetoacetate.
  • the blocking agents (C) are reactive both towards isocyanate groups and also towards epoxy groups. It is therefore preferred that at least one di- or polyisocyanate (A) is first partially reacted with at least one blocking agent (C) and then the remaining free isocyanate groups are at least partially reacted with at least one compound (B). Before the compound (B) is used in the second step, the blocking agent (C) should already have essentially reacted with the isocyanate groups or removed from the reaction mixture.
  • the ratio of epoxy groups in (B) to epoxy-reactive groups in (C) in the polyurethanes according to the invention is generally from 2: 1 to 1: 2, preferably from 1.5: 1 to 1: 1.5, particularly preferred from 1.5: 1 to 1: 1, very particularly preferably from 1.2: 1 to 1: 1.
  • the ratio of isocyanate-reactive groups -XH in (B) and isocyanate-reactive groups in (C) in total to isocyanate groups in (A) is generally chosen so that at least 50 mol% of the isocyanate groups in (A) with compounds (B) and (C) are reacted, preferably at least 66 to 100 mol%, particularly preferably at least 75 to 100 mol%, very particularly preferably at least 85 to 100 mol% and in particular 95 to 100 mol%. In a preferred embodiment, essentially all of the free isocyanate groups in (A) are reacted with isocyanate-reactive groups from (B) and (C).
  • the polyurethanes according to the invention are preferably prepared, in particular the reaction of the compound (B), but also of the compound (C), in the presence of at least one catalyst as listed below.
  • Preferred catalysts are Lewis acidic organic metal compounds such as dibutyltin dilaurate, dioctyltin dilaurate, zinc (II) diacetate, zinc (II) dioctoate, zirconium acetylacetonate and zirconium 2,2,6,6-tetra-methyl- 3,5-heptanedionate and bismuth compounds, for toxicological reasons, especially the non-tin-containing compounds.
  • Lewis acidic organic metal compounds such as dibutyltin dilaurate, dioctyltin dilaurate, zinc (II) diacetate, zinc (II) dioctoate, zirconium acetylacetonate and zirconium 2,2,6,6-tetra-methyl- 3,5-heptanedionate and bismuth compounds, for toxicological reasons, especially the non-tin-containing compounds.
  • the polyurethanes according to the invention are generally produced at temperatures from 40.degree. C. to 130.degree. C., preferably from 50 to 120 and particularly preferably from 60 to 100.degree.
  • At least one solvent is preferably present in the production, which preferably also remains in the coating composition.
  • polyurethanes according to the invention have an NCO content of less than 7% by weight (calculated with a molecular weight of 42 g / mol). In this case, the polyurethanes according to the invention do not require the presence of binders in coating compositions.
  • Polyurethanes of this type can then preferably be used in one-component coating compositions.
  • polyurethanes according to the invention have an NCO content of at least 7% by weight (calculated with a molecular weight of 42 g / mol). This is particularly preferred when at least one binder is added to the polyurethanes of the invention in coating compositions.
  • a solvent or solvent mixture can optionally also be present.
  • Solvents which can be used are those which preferably have no groups which are reactive toward isocyanate groups or blocked isocyanate groups.
  • Possible solvents are e.g. Esters, ethers, ketones, aromatic solvents, alkoxylated alkanoic acid alkyl esters, carbonates, or mixtures of the solvents.
  • Esters are, for example, n-butyl acetate, ethyl acetate, 1-methoxypropyl-2-acetate and 2-methoxyethyl acetate.
  • Ethers are, for example, THF, dioxane and the dimethyl, ethyl or n-butyl ethers of ethylene glycol, diethylene glycol, triethylene glycol, propylene glycol, dipropylene glycol or tripropylene glycol.
  • Ketones are, for example, acetone, ethyl methyl ketone, diethyl ketone, isobutyl methyl ketone, methyl amyl ketone and tert-butyl methyl ketone. Acetone is less preferred because of its flash point.
  • Particularly preferred aromatic hydrocarbons are xylene and toluene, in particular xylene.
  • Solvesso® brands from ExxonMobil Chemical, especially Solvesso® 100 (CAS No. 64742-95-6, predominantly Cg and C 10 aromatics, boiling range about 154 - 178 ° C), 150 (boiling range about 182 -207 ° C) and 200 (CAS No. 64742-94-5), as well as the Shellsol® brands from Shell, Caromax® (e.g. Caromax® 18) from Petrochem Carless and Hydrosol from DHC (e.g. as Hydrosol ® A 170).
  • butyl glycol diacetate Merk Schuchardt OHG
  • butyl glycol acetate Merk Schuchardt OHG
  • dipropylene glycol dimethyl ether Proglyde® DMM, Sigma-Aldrich, Germany
  • 3-methoxy-n-butyl acetate butoxyl, FB Silbermann GmbH
  • dipropylene glycol butyl ether BDG, Dowanol® DPnB, Dow Chemical Company
  • Alcohols can also be used as solvents, but the amount should be kept small, especially when it comes to monofunctional alcohols. Alcohols are less preferred.
  • Preferred solvents are n-butyl acetate, ethyl acetate, 1-methoxypropyl-2-acetate, 2-methoxyethyl acetate, xylene, toluene, and mixtures thereof.
  • UV stabilizers such as UV absorbers and suitable radical scavengers (in particular HALS compounds, hindered amine light stabilizers), activators (accelerators), drying agents, fillers, pigments, dyes, antistatic agents, flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents.
  • suitable radical scavengers in particular HALS compounds, hindered amine light stabilizers
  • activators accelerators
  • drying agents fillers, pigments, dyes, antistatic agents, flame retardants, thickeners, thixotropic agents, surface-active agents, viscosity modifiers, plasticizers or chelating agents.
  • UV stabilizers are preferred.
  • Suitable UV absorbers include oxanilides, triazines and benzotriazole (the latter available e.g. as Tinuvin® brands from BASF SE) and benzophenones (e.g. Chimassorb® 81 from BASF SE).
  • Preferred are e.g. 95% benzene propanoic acid, 3- (2H-benzotriazol-2-yl) -5- (1,1-dimethylethyl) -4-hydroxy, C7-9 branched and linear alkyl esters; 5% 1-methoxy-2-propyl acetate (e.g.
  • radical scavengers for example sterically hindered amines (often also referred to as HALS or HAS compounds; hindered amines (light) stabilizers) such as 2,2,6,6-tetramethylpiperidine, 2,6-di-tert .-Butylpiperidine or its derivatives, e.g. B. bis (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate can be used.
  • HALS or HAS compounds hindered amines (light) stabilizers
  • 2,2,6,6-tetramethylpiperidine, 2,6-di-tert .-Butylpiperidine or its derivatives, e.g. B. bis (2,2,6,6-tetra-methyl-4-piperidyl) sebacinate can be used.
  • suitable radical scavengers for example sterically hindered amines (often also referred to as HALS or HAS compounds; hindered amines (light) stabilizers
  • hindered amines which are N-alkylated, for example bis (1,2,2,6,6-pentamethyl-4-piperidinyl) - [[3,5-bis (1, 1-dimethylethyl) -4-hydroxyphenyl] methyl] butyl malonate (for example Tinuvin® 144 from BASF SE); a mixture of bis (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate and methyl (1,2,2,6,6-pentamethyl-4-piperidinyl) sebacate (e.g.
  • Tinuvin® 292 from BASF SE or the N- (O-alkylated) are, such as decanedioic acid, bis (2,2,6,6-tetramethyl-1- (octyloxy) -4-piperidinyl) ester, reaction products with 1,1-dimethylethylhydroperoxide and octane (e.g. Tinuvin® 123 from BASF SE) UV stabilizers are usually used in amounts of 0.1 to 5.0% by weight, based on the solid components contained in the preparation.
  • organic and inorganic thickeners such as hydroxymethyl cellulose or bentonite are suitable as thickeners.
  • chelating agents e.g. Ethylenediamine acetic acid and its salts as well as ⁇ -diketones can be used.
  • Practically insoluble here means a solubility at 25 ° C. below 1 g / 1000 g of application medium, preferably below 0.5, particularly preferably below 0.25, very particularly preferably below 0.1 and in particular below 0.05 g / 1000 g of application medium.
  • pigments in the proper sense include any system of absorption and / or effect pigments, preferably absorption pigments.
  • the number and selection of the pigment components are not subject to any restrictions. They can be adapted as required to the respective requirements, for example the desired color impression, for example as described in step a).
  • all pigment components of a standardized mixed paint system can be the basis.
  • Effect pigments are to be understood as meaning all pigments which have a platelet-shaped structure and give a surface coating special decorative color effects.
  • the effect pigments are, for example, all effect pigments which can usually be used in vehicle and industrial painting.
  • Examples of such effect pigments are pure metal pigments; such as aluminum, iron or copper pigments;
  • Interference pigments such as, for example, titanium dioxide-coated mica, iron oxide-coated mica, mixed oxide-coated mica (for example with titanium dioxide and Fe 2 O 3 or titanium dioxide and Cr 2 O 3 ), metal oxide-coated aluminum, or liquid crystal pigments.
  • the coloring absorption pigments are, for example, customary organic or inorganic absorption pigments which can be used in the paint industry.
  • organic absorption pigments are azo pigments, phthalocyanine, quinacridone and pyrrolopyrrole pigments.
  • inorganic absorption pigments are iron oxide pigments, titanium dioxide and carbon black.
  • Dyes are also colorants and differ from pigments in their solubility in the application medium, i.e. at 25 ° C they have a solubility of over 1 g / 1000 g in the application medium.
  • dyes examples include azo, azine, anthraquinone, acridine, cyanine, oxazine, polymethine, thiazine, triarylmethane dyes. These dyes can be used as basic or cationic dyes, mordant, direct, dispersion, developing, vat, metal complex, reactive, acid, sulfur, coupling or noun dyes.
  • Coloristically inert fillers are all substances / compounds that are coloristically ineffective on the one hand; i.e. which show a low self-absorption and whose refractive index is similar to the refractive index of the coating medium, and which, on the other hand, are able to determine the orientation (parallel alignment) of the effect pigments in the surface coating, i.e. in the applied paint film, and also properties of the coating or the coating compositions, for example hardness or rheology.
  • inert substances / compounds that can be used are named as examples, without, however, restricting the term coloristically inert, topology-influencing fillers to these examples.
  • Suitable inert fillers can be, for example, transparent or semitransparent fillers or pigments, e.g. Silica gels, blancfixe, kieselguhr, talc, calcium carbonates, kaolin, barium sulfate, magnesium silicate, aluminum silicate, crystalline silicon dioxide, amorphous silica, aluminum oxide, microspheres or hollow microspheres e.g. made of glass, ceramic or polymers with sizes of 0.1-50 ⁇ m, for example.
  • any solid inert organic particles such as e.g. Urea-formaldehyde condensation products, micronized polyolefin wax and micronized amide wax can be used.
  • the inert fillers can in each case also be used in a mixture. However, only one filler is preferably used in each case.
  • Preferred fillers include silicates, e.g. B. silicates obtainable by hydrolysis of silicon tetrachloride such as Aerosil® from Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonates, etc.
  • silicates e.g. B. silicates obtainable by hydrolysis of silicon tetrachloride such as Aerosil® from Degussa, silica, talc, aluminum silicates, magnesium silicates, calcium carbonates, etc.
  • a further optional component of the coating compound is a catalyst.
  • at least one catalyst is present. It can be, for example, an amine or, preferably, an organometallic compound. Preferred catalysts are those which also catalyze the deblocking of the polyurethanes according to the invention.
  • Amines are, for example, tertiary aliphatic, cycloaliphatic or aromatic amines. Examples are triethylamine, tri-n-butylamine, N-methylmorpholine, N-methyl piperidine, pyrrolidine, imidazole, quinuclidine, preferably 1,4-di-aza-bicyclo- [2.2.2] octane.
  • tin compounds come into consideration, such as tin (II) salts of organic carboxylic acids, for example tin (II) diacetate, tin (II) dioctoate, tin (II) bis (ethylhexanoate) and Tin (II) dilaurate and the toxicologically questionable dialkyltin (IV) salts of organic carboxylic acids, e.g.
  • Lewis acidic organic metal compounds are zinc salts, for example zinc (II) diacetate and zinc (II) dioctoate.
  • tin- and zinc-free alternatives preferred include organic metal salts of bismuth, zirconium, titanium, aluminum, cerium, cesium, iron, manganese, nickel and cobalt are used.
  • Zirconium tetraacetylacetonate e.g. K-KAT® 4205 from King Industries
  • Zirconium dionates e.g. K-KAT® XC-9213; XC-A 209 and XC-6212 from King Industries
  • Bismuth compounds, in particular tricarboxylates e.g. K-KAT® 348, XC-B221; XC-C227, XC 8203 from King Industries
  • Aluminum dionate e.g. K-KAT® 5218 from King Industries.
  • Tin- and zinc-free catalysts are otherwise used e.g. also offered under the trade name Borchi® Kat from Borchers, TK from Goldschmidt or BICAT® from Shepherd, Lausanne.
  • Bismuth catalysts are, in particular, bismuth carboxylates, especially bismuth octoates, ethylhexanoates, neodecanoates or pivalates; for example K-KAT 348 and XK-601 from King Industries, TIB KAT 716, 716LA, 716XLA, 718, 720, 789 from TIB Chemicals and those from Shepherd Lausanne, as well as catalyst mixtures from e.g. Bismuth and zinc organyls.
  • catalysts are suitable for solvent-based, water-based and / or blocked systems, depending on the situation.
  • Molybdenum, tungsten and vanadium catalysts are used in particular for the conversion of blocked polyisocyanates WO 2004/076519 and WO 2004/076520 described.
  • Preferred Lewis acidic organic metal compounds are dibutyltin dilaurate, dioctyltin dilaurate, zinc (II) diacetate, zinc (II) dioctoate, zirconium acetylacetonate and zirconium 2,2,6,6-tetramethyl-3,5 -heptanedionate and bismuth compounds, for toxicological reasons, especially the non-tin-containing compounds.
  • the substrates are coated by customary methods known to those skilled in the art, at least one coating compound being applied to the substrate to be coated in the desired thickness and the optionally present volatile constituents of the coating compound being removed, optionally with heating. This process can be repeated one or more times if desired.
  • the application to the substrate can be carried out in a known manner, e.g. B. by spraying, troweling, knife coating, brushing, rolling, rolling, pouring, lamination, back injection or coextrusion.
  • the thickness of such a layer to be hardened can be from 0.1 ⁇ m to several mm (e.g. (structural) adhesives, pourable floors, primers, fillers). Preference is given to 5 to 200 ⁇ m, particularly preferably 5 to 60 ⁇ m, particularly preferably 20-50 ⁇ m (based on the coating in the state in which the solvent has been removed from the system).
  • coatings with a thickness of 0.5 to 10 mm can be obtained with the aid of the coating compositions according to the invention.
  • the blocking agent split off from the coating does not lead to the formation of bubbles in the coating compositions according to the invention.
  • the polyurethane coatings according to the invention are produced by applying to a substrate at least one polyurethane according to the invention, optionally mixed with at least one further polyisocyanate, as listed above under compound (A), which is different from the polyurethane according to the invention, and heating it to a temperature at which at least some of the blocked isocyanate groups are significantly split into free isocyanate groups and free blocking agent (C).
  • “Significant” here means at least 10 mol% of the blocked isocyanate groups, preferably at least 25, particularly preferably at least 40, very particularly preferably at least 50, in particular at least 66 and especially at least 75 mol%.
  • the temperature for curing the coating and deblocking depends in each case on the blocking agent (C) used and can preferably be from 100 to 160.degree.
  • the duration is generally from 5 minutes to 3 hours, preferably 10 minutes to 2.5 hours and particularly preferably 15 minutes to 2 hours.
  • the blocking agent (C) is released from the blocked isocyanate group, so that the isocyanate group which is now free is available for reaction, and the blocking agent reacts with the epoxy group of component (B).
  • the blocking agent (C) is released from the blocked isocyanate group and reacts with the epoxy group of component (B).
  • the hydroxyl group which forms in this reaction with the epoxy group then reacts with a free isocyanate group to form a urethane group.
  • a further optional component of such coating compositions can be a further polyisocyanate (D) which is different from the polyurethane according to the invention and which can be di- or polyisocyanates as described above under component (A).
  • D further polyisocyanate
  • the present invention also relates to substrates coated with a coating material according to the invention.
  • Polyurethane lacquers of this type are particularly suitable for applications in which a particularly high level of application reliability, outdoor weather resistance, optics, solvent, chemical and / or water resistance are required.
  • the two-component coating compositions and paint formulations obtained are suitable for coating substrates such as wood, wood veneer, paper, cardboard, cardboard, textiles, foil, leather, fleece, plastic surfaces, glass, ceramics, mineral building materials such as cement blocks and fiber cement boards or metals, the each can optionally be pre-coated or pre-treated.
  • the choice of substrate is usually limited by its thermal stability, so that those substrates are preferred which are stable under the unblocking conditions.
  • Such coating compounds are suitable as or in internal or external coatings, i.e. those applications that are exposed to daylight, preferably of parts of buildings, Coatings on (large) vehicles and aircraft and industrial applications, commercial vehicles in the agricultural and construction sectors, decorative paintwork, bridges, buildings, electricity pylons, tanks, containers, pipelines, power plants, chemical plants, ships, cranes, piles, sheet piling, fittings, pipes, Fittings, flanges, couplings, halls, roofs and structural steel, furniture, windows, doors, parquet, can-coating and coil-coating, for floor coverings such as on parking decks or in hospitals in automotive paints as OEM and refinish applications.
  • internal or external coatings i.e. those applications that are exposed to daylight, preferably of parts of buildings, Coatings on (large) vehicles and aircraft and industrial applications, commercial vehicles in the agricultural and construction sectors, decorative paintwork, bridges, buildings, electricity pylons, tanks, containers, pipelines, power plants, chemical plants, ships, cranes, piles
  • ppm and percentages used in this document relate to percentages and ppm by weight.
  • Basonat® HI 100 commercially available from BASF SE, Ludwigshafen, polyisocyanate containing isocyanurate groups based on 1,6-hexamethylene diisocyanate with an NCO content of 21.8% and a viscosity of 2800 mPa * s at 23 ° C.
  • the samples were applied to glass plates in a wet layer thickness of 400 ⁇ m, flashed off at room temperature for 15 minutes and cured at the temperature and duration indicated in the table.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Wood Science & Technology (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Paints Or Removers (AREA)

Claims (12)

  1. Polyuréthanes, pouvant être obtenus par mise en réaction de
    (A) au moins un di- ou polyisocyanate aliphatique ou cycloaliphatique,
    (B) au moins un composé contenant au moins un, de préférence exactement un groupe hydroxy ou thiol et au moins un groupe époxy, ainsi que
    (C) au moins un agent bloquant contenant un groupe qui est réactif aussi bien vis-à-vis d'un groupe isocyanate que vis-à-vis d'un groupe époxy,
    le composé (C) étant choisi dans le groupe constitué par :
    - les amines secondaires cycliques, les dialkylamines en C1-C10 et les di-cycloalkylamines en C6-C12, de préférence la diéthylamine, la diisopropylamine, la méthylisopropylamine, la méthylbutylamine, la 2,6-diméthylpipéridine, les dicyclohexylamines, la bis(3,5,5-triméthylcyclohexyl)amine et la 2,2,6,6-tétraméthylpipéridine,
    - les lactames,
    - en particulier la 2-pyrrolidone et le caprolactame,
    - les oximes,
    - en particulier les oximes de méthyl-n-amylcétone, méthylisoamylcétone, méthyl-3-éthylheptylcétone, méthyl-2,4-diméthylpentylcétone, butanone (méthyléthylcétone), cyclohexanone, méthylisopropylcétone, méthylisobutylcétone, diisobutylcétone, méthyl-t-butylcétone, diisopropylcétone et 2,2,6,6-tétraméthylcyclohexanone, de manière particulièrement préférée le butanone-oxime (méthyléthylcétone-oxime),
    - les pyrazoles,
    - en particulier le 3,5-diméthylpyrazole,
    - les triazoles,
    - en particulier les 1,2,4-triazoles,
    - les composés de 1,3-dicarbonyle,
    - en particulier l'acétylacétone, l'ester dialkylique en C1-C10 de l'acide malonique et l'ester alkylique en C1-C10 de l'acide acétoacétique, de manière particulièrement préférée l'ester diéthylique de l'acide malonique et l'ester éthylique de l'acide acétoacétique.
  2. Polyuréthanes selon la revendication 1, caractérisés en ce que le composé (A) est choisi dans le groupe constitué par le diisocyanate d'isophorone, le 2,4'-di(isocyanatocyclohexyl)méthane et le 4,4'-di(isocyanatocyclohexyl)méthane, ainsi que leurs mélanges.
  3. Polyuréthanes selon la revendication 1, caractérisés en ce que le composé (A) est choisi dans le groupe constitué par les polyisocyanates contenant des groupes isocyanurate à base de diisocyanate de 1,6-hexaméthylène et/ou de diisocyanate d'isophorone et les polyisocyanates contenant des groupes biuret à base de diisocyanate de 1,6-hexaméthylène.
  4. Polyuréthanes selon la revendication 3, caractériséss en ce qu'il présente la formule (II)
    Figure imgb0029
     où
    R1 représente à chaque fois 1,6-hexylène,
    Figure imgb0030
     de préférence 1,6-hexylène, et
    Z1, Z2 et Z3 sont chacun choisis indépendamment les uns des autres dans le groupe constitué par :
    - un groupe isocyanate libre (-NCO),
    - un groupe isocyanate bloqué et
    - un groupe de la formule (III)
    Figure imgb0031
    où
    X représente oxygène (O) ou soufre (S), et
    n représente un nombre entier positif de 1 à 3, de préférence 1 ou 2, et de manière particulièrement préférée 1, et
    R2 représente un espaceur (n+1)-valent, comprenant 1 à 10 atomes et/ou groupes d'atomes,
    au moins un des groupes Z1 à Z3 étant un groupe isocyanate bloqué et au moins un des groupes Z1 à Z3 étant un groupe de la formule (III).
  5. Polyuréthanes selon la revendication 3, caractérisés en ce qu'il présente la formule (IV)
    Figure imgb0032
     où
    Bloc représente un radical d'un agent bloquant (C), duquel un atome d'hydrogène est soustrait,
    X représente oxygène (O) ou soufre (S),
    R1 représente à chaque fois 1,6-hexylène,
    Figure imgb0033
     de préférence 1,6-hexylène,
    n représente un nombre entier positif de 1 à 3, de préférence 1 ou 2, et de manière particulièrement préférée 1, et
    R2 représente un espaceur (n+1)-valent, comprenant 1 à 10 atomes et/ou groupes d'atomes.
  6. Polyuréthanes selon la revendication 3, caractérisés en ce qu'il présente la formule (V)
    Figure imgb0034
     où
    Bloc représente un radical d'un agent bloquant (C), duquel un atome d'hydrogène est soustrait,
    X représente oxygène (O) ou soufre (S),
    R1 représente à chaque fois 1,6-hexylène,
    n représente un nombre entier positif de 1 à 3, de préférence 1 ou 2, et de manière particulièrement préférée 1, et
    R2 représente un espaceur (n+1)-valent, comprenant 1 à 10 atomes et/ou groupes d'atomes.
  7. Polyuréthanes selon l'une quelconque des revendications précédentes, caractérisés en ce qu'ils présentent une teneur en NCO de moins de 7 % en poids (calculée avec un poids moléculaire de 42 g/mol).
  8. Matériau de revêtement, contenant :
    - au moins un polyuréthane selon l'une quelconque des revendications précédentes,
    - éventuellement des solvants,
    - éventuellement des additifs typiques des vernis, ainsi que
    - éventuellement au moins un catalyseur.
  9. Matériau de revêtement selon la revendication 7, caractérisé en ce que le catalyseur consiste en du dilaurate de dibutylétain, du dilaurate de dioctylétain, du diacétate de zinc (II), du dioctoate de zinc (II), de l'acétylacétonate de zirconium et du 2,2,6,6-tétra-méthyl-3,5-heptanedionate de zirconium ou des composés de bismuth.
  10. Procédé de fabrication de polyuréthanes selon les revendications 1 à 6, caractérisé en ce qu'au moins un di- ou polyisocyanate (A) est tout d'abord mis en réaction partiellement avec au moins un agent bloquant (C), puis les groupes isocyanate libres restants sont mis en réaction au moins partiellement avec au moins un composé (B).
  11. Procédé de fabrication de revêtements de polyuréthane, caractérisé en ce qu'au moins un polyuréthane selon l'une quelconque des revendications 1 à 7, éventuellement mélangé avec au moins un polyisocyanate supplémentaire, qui est un autre que le polyuréthane, est appliqué sur un substrat, et porté à une température à laquelle au moins une partie des groupes isocyanate bloqués est significativement clivée en groupes isocyanate libres et agent bloquant libre (C) .
  12. Utilisation de polyuréthanes selon l'une quelconque des revendications 1 à 7 dans des matériaux de revêtement monocomposants.
EP14766119.3A 2013-09-25 2014-09-03 Nouveaux agents de réticulation pour matières de revêtement Active EP3049455B1 (fr)

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DE3314790A1 (de) 1983-04-23 1984-10-25 Basf Ag, 6700 Ludwigshafen Mehrstufenverfahren zur herstellung von 3-isocyanatomethyl-3,5,5-trimethyl-cyclohexylisocyanat
DE3314788A1 (de) 1983-04-23 1984-10-25 Basf Ag, 6700 Ludwigshafen Mehrstufenverfahren zur herstellung von hexamethylendiisocyanat-1,6 und/oder isomeren aliphatischen diisocyanaten mit 6 kohlenstoffatomen im alkylenrest
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